Vapor purification and cracking method, and apparatus, for petroleum oils



Aug. 3, 1937- OCON 2,088,756

VAPOR PURIFICATION AND CRACKING METHOD AND APPARATUS FOR PETROLEUM OILS Filed June 15, 1935 2 Sheets-Sheet 1 mm M INVENTOR. m .4. (9 I ATTORNEY.-

Aug. 3,

E. A. OCON 2,088,7 56

VAPOR PURIF ICATION AND CRACKING METHOD vAND APPARATUS FOR PETROLEUM OILS 2 Sheets-Sheet 2 Filed "June 15 1935 INVENTOR.

ATTORNEY.

Patented Aug. 1937 varoa ruamca'rron AND "CRACKING amnion, m arraas'rus, FOR ra'mo- LEUM OILS Ernest A. Ocon, New York, N. y.

Application June 15,

16 Claims.

I reduction of viscosity, and the vapors are separated from the unvaporized oil simultaneously .with a desulfurizing treatment, the vaporized product 'thus reduced in viscosity and substantially desulfurized is passed to-two cracking coils receiving diiferentdegrees of thermal treatment,

and in the coil receiving the highest thermal treatment, the said vapors meet the previously heated but unvaporimd oil of the initial charging stock together with heavy liquid fractions remaining after the blending of vapors from the the vapors are reduced in temperature, de,-' gummed and separated from heavier fractions,

gothe vapors thenpassing to a flnal catalyst which may be of the desulfurizing type when required, or of the hydrogenating type when desulfurizin action is not required, the vapors then passing to a fractionating tower.

An anti-detonating material such as alkyl benzene, nitro-benzol, ethyl benzol, ethylbenzene, nitrous-ether, isopropyl benzene with alcohol in my preferred practice may be sprayed into the vapors, and in either vapor or liquid form, 40 singly or in admixture.

*In either phase of the invention where the breaking down of viscosity is not required and the sulfur content is low, the process is modified accordingly, thesame principle applies to both 45 phases, 1. e., when the charging stock is vaporized and is led-to a manifold from which two streams are led, each to an individual coil, the coil of highest heat receiving the unvaporized poitions of the initial heated charging stock, the '50 products discharged from'both coils being blended, cooled, and subjected to catalytic treatment, and are degummed prior to fractionation where degumming is required, the cooling and degum- I ming chamber being utilized as a separator for 55 the heavy and condensed fractions which are led 1935, Serial No. 26,835 (c1. lac-e1 back to the cracking coil ofhighest heat jointly -with the originally heated but unvaporized charging stock. 1

The invention will be described with reference to the accompanying drawings, in which:

Figure 1 is a schematic view in elevation showing an apparatus for carrying the method into effect, and

Figure 2 is a view similar to Fig. 1, showing a modified form of the apparatus. 10 g In the apparatus illustrated in the drawings, a charging stock is led by pipe I to a preheating coil 2 and thence to a second preheating coil 3, the heated charging stock passing into viscosity breaker tanki.

Within tank 6 are baflies 6 below which there may be discharged from tank I a desulfurizin agent through pipe 8. Tank 5 receives a highly heated blast of cracked oil-steam vapors by means of a pipe 9 having a let it, the pipe communicating with the discharge outlet of a cracking coil later to be described.

Also within the viscosity breaker tank 5 near the top thereof may be a body of catalytic material ii preferably of the desuliurizing type. By

means of preheating coils 2 and 8, plus the .heat

added to tank 5 by the blast of highly heated vapors through jet member i0 and also external heat to be later'described, the charging stock in tank 5 is raised to substantially vapor form. The vapors pass upwardly through desuiinrizing material ii and out through pipe ii, the unvaporized fractions dropping and being discharged as later to be described. The vapors reduced in viscosity by the heat treatment and the jet of oil steam' vapors and the sulfur content being substantially reduced, leave pipe I! and 'pass to a manifold it. The upper end of the manifold discharges into a cracking coil ll, and the lower end of the manifold discharges into a cracking coil 40 Hz, the cracking coils being disposed within a vkiln c Steam is injected into the coils simultaneously. with the pre-treated vapors by means of pipe II and branch pipe i1, "0:. The vapor temperature 43 within the coil of highest heat, to wit, llz, may be-1200-1400 F. and the vapor temperature in coil ll may be 900-1200 F. Coil II at its discharge end may recelve metallic catalyst l8 and coil :1: may receive metallic catalyst llx. Ad- 'jacent the catalysts the coils have discharge branches communicating with a blending chamv her I! which may receive 'a sulfur reagent material through pipe 2i and a sulfur absorbent material through pipe 20.

required by the battles 24:, and thence being discharged by pipe II into the base of the fractionating tower 20.

'I'he-unvaporized treated oil is carried off through pipe 21:: to the inlet of the coil of highest heat, llx, and any heavy residue and spent sludge dropped to the bottom of tank 22 and are I carried off by pipe 21 and branch pipe 44.

The fractionating tower may receive through a jet communicating with pipe I. at the top of the tower an antl-detonating material in either liquid or vapor form such as one or a mixture of materials selected from alkyl benzene, nitro-benzol, ethyl benzol, ethylbenzene, nitrous-ether, 180- propyl benzene. The gasoline vapors leave the tower overhead through pipe- II, the light distillates leave the tower through pipes ii and 3 2 and tower bottoms are'withdrawn through pipe 33 by the action of pump 34 passing thence to a charging stock conduit, one being mixed with the charging stock about to pass through the preheater coil 3. Any sludge settling at the bottom of the tower is ejected through pipe 31 and pipe 44. c

- The unvaporized heavy oil fractions within viscosity breaker tank I are withdrawn-through.

pipe 38, trap 39 and pipe: to pump ll which passes said heavy fractions substantially free from sludge, into the second trap 43 and thence to the coil receiving the highestdegree of heat, "1:. Any sludge in trap Il may be discharged through pipe :1: .and in trap 48 may be discharged by means of pipe ll.

By means of branch pipe I! suitably controlled by the valve, a small portion of the tower bottoms may be passed into the steam line ll;

In the practice of the method, treating oi sulfur-containing oil, the charging stock is fed into the viscosity breaker I wherein a temperature 50 of 500-750 I". may be maintained by the application of heat. The action of the preheating coils 2 and 3 will preheat the charging stock, for example, to 250 F. and this temperature will be raised in the viscosity breaker first by a blast of highly heated'cracking oil-steam vapors and also,

if required, a suitable heat application, as by passage of the products to the kiln through a chamber 40 surrounding the viscosity breaker. Thus the charging stock will be substantially no vaporized and its vapors will passupwardlyinto only a viscosity breaker but is a separation chasm 7 her by means of which the heavier unvaporised portion of the charging stock is separated from the vaporized portion. The vaporized portion of .the charging stock which I prefer to be in much greater proportion, passes to a manifold preferably vertically arranged, communicating with aoeavsc cracking coil ll of lesser heat and cracking coil .1: of maximum-heat, simultaneously. In other words, the vapors treated in the viscosity breaker may be'split into two streams which simultaneously enter the cracking coils, one stream receiving higher heat treatment than the second stream. In or prior to entering the cracking coils pipe I! and also may receive a regulated flow oi tower bottoms pumped through by-pass 36 into the steam coil II; The temperature in the coil ll: of maximum heat may be 1200-1400" F. and in the coiiof lesser heatlkmay be 900-l200 F. The discharge end of each coil may project exteriorly of the kiln and have disposed therein catalytic material it, its, respectively, which may be of the hydrogenation type. These catalysts are not essential, however, in all cases.

From the discharge end of each coil the vapors enter into the blending section of a purifying chamber which in the drawings comprises section IO. Into the vapors within the blending section I iniect (through pipe 2|) a sulfur reagent material such as ammonium sulfide, ammonium chloride, zinc chloride in liquid or vapor form in order to accelerate the subsequent adsorption.

(through pipe 20) From the blending section the vapors are passed upwardly in chamber 22 through adsorp-- ent material 23 which may be infu'sorial earth, fuller's earth, bauxite, silica'gel, Florida earth, quartz, bentonite or other suitablematerial. The temperature of the vapors is lowered by radiation from the walls of members is, 22, and by absorption by the heat exchange-member 2. The vapors are purified and degummed by the adsorbent material 23 and the absorbed sulfur passes with the spent sludge to the base of tank 1!, passing on through pipe 21. Level of the liquid in the lower portion of tank 22 is controlled by a valve near the top of pipe 21 so that therewill be a constant flow of purified condensate, substantially free from tarry material,

through pipe 21:: to the cracking coil of highest heat.

The purified vapors leaving the adsorbent materlal 23 reach the top of the tank and pass through catalytic material 24, the catalysts used being one or a compound of two or more oxides and/or sulfides selected from metals such as tungsten, nickel, chromium, molybdenum, aluminum,'titanium, magnesium, calcium, cobalt, zinc and the like. Iron sulfides, particularly the heavy metal sulfides, will advantageously be added to the catalysts which may be 'in any desired.

form such as beads, rings, baiiles, wire gauze or in the form of lamps, briquettes, blocks; and may be mixed to a binder such as lime, clay, cement, and the like,'and/or may be added advantageously to the charging stock in a finely divided form.

when the sulfur contentis higher, the catalysts may be selected for desuifurizing properties. The, cracked and purified vapors then pass'into the fractiohating tower and if necessary the temperature of the vapors may be raised and the vapors sweetened by the injection of steam into the base of the fractionating tower through pipe 20. As aforesaid, anti-detonating material may bedniected into the vapors within the fractionating tower through pipe 30.

The vapors are fractionated and condensate may partly be used as fuel, as, for example, part hi the heavy condensate, or returned to the charging stock in the manner described above (pipe 33 and pump 34).

When desulfurization is not required, the use '0'! the adsorbent and absorbent material may be employ highly heated material from a separate source.

It is to be noted that the steam injected into the intake end of each cracking coil may be superheated, as, for example, by means of a superheating coil l6 located directly within the cracking kiln. The manifold l3 may be of any desired diameter and of uniform diameter or of greater diameter in the section l3x.

Pressure upon one cracking coil may be varied with respect to the second coil by means of the valves film, Max. The cracking tubes may be of a length required for the general nature of the charging stock employed and the time of reaction may be controlled by the valves 41, 412, so that the time of reaction in one coil may be greater or less than that of the second coil. The valves in pipe ll, i'fia: may be manipulated to cause injection of more steamin one coil than in the second coil, as, for example, a greater proportion of steam may be injected into the coil i la: receiving the heavier materials, in each case sufiicient to retard polymerization of the oil vapors. The time of the cracking reactions of the oil-steam vapors will be less than thifiy seconds, with pressure below 30 atmospheres, in the embodiment of the invention shown in the drawings.

In a plant of larger capacity the time of the cracking reactions will be correspondingly longer.

Having described my invention, what I claim and desired to secure by Letters Patent, is as follows:

1. In the art of cracking hydrocarbon oils,

subjecting a petroleum stock to substantial vaporization and separating the vapors thus obtained from the unvaporized oil, dividing the vapors into a plurality of streams having the same vaporization temperature and composition, subjecting each stream of vapor separately to cracking under pressure, one stream being sub-e jected to cracking at a higher temperature than the other throughout its cracking reaction, and

subjecting the resultant cracked products, -free' of coke and tar, to fractionation. r

2. In the art of cracking hydrocarbon oils, subjecting a petroleum stock to vaporization by heating the same to'a mild cracking tempera"- ture of about 750 F. by applied heat including the heat of a blast of highly heated cracked oilvapors and steam, thus reducing the viscosity, separating the vapors thus obtained from the unvaporized oil, and simultaneously dividing the vapors into two, streams, subjecting each stream of vapor separately to a higher cracking temperature than that of the original mild cracking temperature, and not exceeding 1400 F., for a time suflicient to substantially crack said stream, un-

7 der pressure, one stream being subjected to term perature substantially higher than the temperature applied to the other stream,- and subjecting the resultant clean cracked products to tractionation. r a

3. A process in accordance with claim 2, in

which the vapors during treatment to reduce viscosity are subjected to thea'ction-oi a desul'furizing absorbent in the presence of a catalyst, for the absorption of sulfur released below cracking temperatures, and after leaving the cracking coils the cracked vapors are subjected to the action of desulfurizing materials within the blending zone, said materials being of the type adapted for sulfur precipitation under.

cracking temperatures of the oil vapors, and thence fractionating the cracked and desulfurized vapors. r

4. A process in accordance with claim 2, in which superheated steam admixed with a small quantity of hydrocarbon oil is injected into the vapor streams entering the cracking coils.

5. In the art of cracking hydrocarbon oils, subjecting a' petroleum charging stock to substantial vaporization and separating the liquid fmm the vapor, directing the vapor into two streams, and

leading each stream through a cracking coil, one

coil being subjected to higher temperature than the second coil, leading the cracked vapors to a blending zone, cooling the vapors and passing them through a zone containing sulfur absorbent material, separating the condensate from the zone of cooling, recycling the condensate through the coil of higher temperature jointly with vapors from the initial charging stock, and fractionating the thus cracked, blended and treated vapors.

6. A process in accordance with claim 5, in which the tower bottoms from the fractionating zone are recycled by passing them into the charging stock stream, and thence with the charging stock into the vaporization zone-preceding the cracking coils. I

7. In the art of cracking hydrocarbon oils, subjecting a petroleum stock to substantial vaporization, separating the liquid from thevapor in the viscosity reducing zone wherein highly heated steam-oil vapors are led, passing into the viscosity reducing zone a, sulfur absorbent material, passingthe said separated chafging stock vapors to a separating column having two outlets, each izing absorbent operable at cracking-temperature of the charging stock vapors, and'thence passing the cracked, blended and .desulfurized .vapors into a fractionating tower, and passing the liquid from the viscosity reducing zone into. thecracking coil of higher temperature jointly with the treated vapors from said viscosity reducingzone. 8. Inthe art of cracking hydrocarbon oils, subjecting a petroleum charging stock to substantial vaporization, separating the liquid from the vapor, dividing the vapor into two streams, subjecting both .streamsof vapor simultaneously to cracking, one stream being subjected to ahigher temperature than the second stream, blending the cracked'vapors from both streams'and leading the cracked and blended vapors to a: fractionation zone wherein said vapors aresubjected to a prepared synthetic liquid spray of antidetonating material, for common condensation,

means for leading liquid from the viscosity breaker to the last named coil, means for heating the last-named coil to a cracking temperature in excess of heat applied to'the other coil, a manifold having separate discharge outlets each connected with one coil, a vapor flow connection from the viscosity breaker to said manifold, a blending chamber receiving cracked vapors from the coils, means for injecting a sulfur absorbent material into said blending chamber, a' purifying chamber receiving the cracked and blended va pors from the blending chamber and having therein means for cooling the vapors together with adsorbent material through which the vapots are caused to flow, and a fractionating tower receiving the treated vapors from the purifying 10. Apparatus constructed in accordance with claim 9, in which the cracking coils are provided with sections projecting laterally of the heating zone for said coils, metallic catalysts of the hydrogenation type disposed within said projected sections, and connections between said projected sections and the blending chamber.

11. Apparatus constructed in accordance with claim 9, in combination with means for conveying tower bottom to the charging stock stream in the passage of the latter to the viscosity breaker.

12. In a process for the production of motor fuel, subjecting a hydrocarbon stock to vaporizachamber.

40 tion and cracking, subjecting the vapors to desulfurizing and action, separating the vapors of gasoline boiling range from the heavier vapors, mixing the gasoline boiling range vapors with a synthetic highly volatile anti-. detonating material without substantially con-' saidvapors,andcondensingthesaid g vapors with the anti-detonating material mixedtherewithtoproduceapurlfledhomo.

geneous anti-detonating motor fuel.

5 13. A prom for producing hydrocarbon prodvaporize a portion of the charging stock, subjecting unvaporized portions of the charging stock to heat and heating said portions 'at cracking temperature; while in a flowing stream in the I of steam to release and form hydrocarbon vapors, I passing thus produced vapors jointly with steam to the vaporization zone to act as a blast of highly heated vapors, withdrawing mixed vapors from the vaporization zone and subjecting them to cracking in a separate cracking zone.

14. In the art of cracking hydrocarbon oils. subjecting a petroleum stock to substantial vaporization and separating the vapors thus obtained from the unvaporized oil, subjecting the vapors to the action of a desulfurizing absorbent for the absorption of sulfur released below cracking tempertures, dividing the vapors into a. plurality of streams having the same vaporlmtion temperature and composition, subjecting each 14 porization in a zone wherein a blast of highly a heated cracked hydrocarbonvapors obtained in the cracking of the oils during the process is injected in a direction countercurrent to the possage of the preheated oils, producing a mixture of cracked and uncracked vapors, separating the vapors thus obtained from residue and tarry material, mixing the vapors withsteam, subjecting the with increase of'heat, to cracking, by passing a stream of said mixture through a coil subjected to heat above the critical cracking temperature of the mixture and wherein said mixture is progressively heated to a maximum, not exceeding 1400 F., under pressure, the mixture reaching its highest temperature at the out let of the coil, passing said mixture at its highest temperature over an hydrogenating catalyst, and subjecting said treated vapors to fractionation.

16. A processof producing hydrocarbon productsinacoordancewithclaimliiinwhichpart ofthemixedvaporsareseparatedfromtheremaining'partandarecrackedinacracking aone separate fromthatinwhichsaidremainingpart of mixed vaporsare progressively heated to eflect substantial cracking thereof, under superatmospheric'pressure range below thirty a,

and subjected to a cracking temperature below 1400 F.andresultingproductsareusedaspart of. the blast of highly heated vapors injected into the expansion tone.

ERNIE! A. OCOR. 

